TW538080B

TW538080B - Process for increasing the adhesion of a polymeric material to a metal surface and used composition thereof

Info

Publication number: TW538080B
Application number: TW090119979A
Authority: TW
Inventors: Donald Ferrier
Original assignee: Macdermid Inc
Priority date: 2000-08-22
Filing date: 2001-08-15
Publication date: 2003-06-21
Also published as: CN100343356C; JP2004517974A; EP1311644B1; CN1447846A; WO2002016524A1; CA2420540A1; DE60115253T2; DE60115253D1; JP4295504B2; ES2252274T3; US6554948B1; EP1311644A1; EP1311644A4; AU2001283048A1

Abstract

A process is described for treating metal surfaces with a composition comprising an oxidizer, an acid, a corrosion inhibitor, a benzotriazole with an electron withdrawing group in the 1-position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group, and optionally, a source of adhesion enhancing species selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium, vanadium, and combinations of any of the foregoing in order to increase the adhesion of polymeric materials to the metal surface.

Description

538080 五、發明説明（1 ) 發明背景本發明乃有關印刷電路，更具體而言是有關多層印刷電路之製法。由於電子器材的輕薄短小趨勢，使得具一或多層電路之印刷電路應用日廣。在典型多層印刷電路之製程中，先使銅箔被覆之介電基材塗覆光阻劑後製做所欲電路圖案之正像’接著蝕刻除去曝露之銅，移除光阻劑層後，遺留所欲的銅電路圖。任一類型的電路圖之一或多種線路內層及構成接地面及動力面之線路內層均可組裝成多層電路，其方法是在電路內層之間***一或多層部分硬化之介電基材（即所謂之”預浸料还層”” P r e p r e g 1 a y e 1· ”），而形成電路內層和介電基材層交互貼合之複合層，此複合層經熱及壓力處理而使部分硬化基材進一步硬化，使電路內層粘合在一起。如此硬化之複合層有許多穿孔，然後將穿孔敷金屬而使所有的電路層相通。在穿孔敷金屬的過程中，於多層複合材料之最外面層典型上亦同時製作所欲之電路圖案。形成多層印刷電路之另法是利用添加法或表面層合電路法。此等技術是先形成不導電之基材，然後鍍上電路成分。在電路圖上重覆地加上可顯像之塗層，並在可顯像之塗層再鍍上電路。長久以來已知電路內層之銅金屬和硬化預浸料坯層 538080 五、發明説明（2 ) 或其他會接觸之非導電塗層之間所形成的粘合力乃有待努力之空間，因爲硬化之多層複合材料或塗層在其後的加工及/或應用中容易剝離。爲解決此問題，被開發出來的技術包含在將預浸料坯層組成多層複合材料之前，就在電路內層之銅表面形成氧化銅層，例如是使銅表面做化學的氧化。早期此方面的努力使得最後多層電路中之電路內層和介電基材層的粘合力比沒有氧化銅層者小有改善。其後的黑氧化物技術之修改包含先在銅表面上形成黑氧化物塗層，然後以1 5 %硫酸做黑氧化物沈積層做後處理，而得做爲粘著促進劑之紅色氧化物，參閱 A.G· Osborne氏”形成內層用之紅色氧化物之另法”， 1 9 84年8月，以及各種直接形成紅色氧化物接著促進劑之方法，均有不同程度之改良。技藝上最大的改良乃 Landau氏之美國專利4，409,037及4,844,981號，乃由相當多的亞氯酸鹽/相當少的苛性銅氧化組成物形成氧化物，結果使電路內層粘合力有實質的改善。如前所述，組合及硬化之多層電路複合材料具有穿孔’且敷上金屬以便使電路層導電相通，穿孔之敷金屬包含刮除孔面之樹脂，觸媒活化，無電沈積銅，用電解鑛銅等步驟。許多此等製程採用例如酸之介質，其可使氧化銅接著促進劑塗在穿孔上或靠近穿孔部分之內層。由穿孔處有粉紅圈或暈環（其乃因底層的銅金屬露出來） ’可知氧化銅局部的溶解，其也導致多層電路之局部脫層。 _4- 538080 五、發明説明（3 ) 技術上已注意此”粉紅圈”現象，並花很大的功夫尋求之不易產生此種局部脫層之多層印刷電路的製程。有人建議採用粘著促進氧化銅之厚塗層，以免在其後的加工只因氧化銅層太薄而溶解。如此實質上對生產力有妨害，因爲氧化物塗層太厚時，接著促進效果會變差。另項建議是組裝多層複合材料之壓縮/硬化條件的最適化，但其效果仍有限。解決此問題之另一方法是在組裝電路內層和預浸料坯層成爲多層複合材料之前，先對氧化銅接著促進塗層做後處理。例如Cordani氏之美國專利4,775,444號發表的方法是在電路內層之銅表面先塗氧化銅，然後在電路內層參與多層組裝之前，接觸鉻酸水溶液。此項處理可使氧化銅塗層安定化及/或防止在其後加工步驟（如穿孔敷金屬）中溶於酸性介質，於是可使粉紅圈/脫層可能性最小化。 ‘538080 V. Description of the Invention (1) Background of the Invention The present invention relates to printed circuits, and more specifically to a method for manufacturing multilayer printed circuits. Due to the thinness and shortness of electronic equipment, printed circuits with one or more layers of circuits are widely used. In a typical multi-layer printed circuit manufacturing process, a copper foil-covered dielectric substrate is coated with a photoresist, and then a positive image of a desired circuit pattern is made. Then, the exposed copper is removed by etching, and the photoresist layer is removed. Leave the desired copper circuit diagram. One or more of the inner layers of any type of circuit diagram and the inner layers of the lines that make up the ground and power planes can be assembled into a multilayer circuit by inserting one or more partially hardened dielectric substrates between the inner layers of the circuit (That is, the so-called "prepreg return layer" "Prepreg 1 aye 1 ·"), and a composite layer of the inner layer of the circuit and the dielectric substrate layer is formed, and this composite layer is partially treated by heat and pressure The hardened substrate is further hardened to bond the inner layers of the circuit together. The composite layer thus hardened has many perforations, and the perforations are then metallized to communicate all the circuit layers. In the process of perforating metallization, the desired circuit pattern is typically also made on the outermost layer of the multilayer composite material at the same time. Another method of forming a multilayer printed circuit is to use an additive method or a surface-laminated circuit method. These techniques first form a non-conductive substrate and then plate the circuit components. Developable coatings are repeatedly applied to the circuit diagram, and circuits are applied to the developable coatings. It has been known for a long time that the inner layer of copper metal and the hardened prepreg layer 538080 V. Description of the invention (2) or other non-conductive coatings that will come in contact with each other need to be worked hard because of the hardening The multilayer composite material or coating is easily peeled off during subsequent processing and / or applications. In order to solve this problem, the technology developed includes forming a copper oxide layer on the copper surface of the inner layer of the circuit before the prepreg layer is formed into a multilayer composite material, for example, chemically oxidizing the copper surface. Early efforts in this area improved the adhesion between the inner layers of the circuit and the dielectric substrate layer in the final multilayer circuit compared to those without the copper oxide layer. Subsequent modifications of the black oxide technology include forming a black oxide coating on the copper surface, and then post-processing with a 15% sulfuric acid as a black oxide deposition layer to obtain a red oxide as an adhesion promoter. See AG · Osborne's "An Alternative Method for Forming Red Oxides for the Inner Layer", August 1984, and various methods of directly forming a red oxide followed by an accelerator, which have been improved to varying degrees. The biggest improvement in technology is Landau's U.S. Patent Nos. 4,409,037 and 4,844,981, which form oxides from a relatively large amount of chlorite / a relatively small amount of caustic copper oxide composition. As a result, the adhesion of the inner layer of the circuit is substantial. Improvement. As mentioned above, the combined and hardened multilayer circuit composite material has perforations and is coated with metal to make the circuit layer conductive. The perforated metallization includes scraping the resin from the hole surface, activating the catalyst, electrolessly depositing copper, and using electrolytic ore. Copper and other steps. Many of these processes use a medium such as an acid, which enables copper oxide followed by an accelerator to be applied to or near the inner layer of the perforated portion. According to the pink circle or halo ring (which is exposed due to the underlying copper metal) at the perforation, it can be seen that the local dissolution of the copper oxide also leads to the local delamination of the multilayer circuit. _4- 538080 V. Description of the Invention (3) The technology has paid attention to this "pink circle" phenomenon, and has worked hard to find a multilayer printed circuit process that does not easily cause such partial delamination. It has been suggested to use a thick coating of adhesion-promoting copper oxide to prevent subsequent processing from dissolving just because the copper oxide layer is too thin. This is essentially a hindrance to productivity, because when the oxide coating is too thick, the subsequent promotion effect will be poor. Another suggestion is to optimize the compression / hardening conditions for assembling multilayer composites, but their effectiveness is still limited. Another way to solve this problem is to post-process copper oxide and then promote the coating before assembling the inner layer of the circuit and the prepreg layer into a multilayer composite. For example, U.S. Patent No. 4,775,444 issued by Cordani's method is to first apply copper oxide to the copper surface of the inner layer of the circuit, and then contact the aqueous solution of chromic acid before the inner layer of the circuit participates in multi-layer assembly. This treatment stabilizes the copper oxide coating and / or prevents dissolution in acidic media during subsequent processing steps (such as perforation metallization), thereby minimizing the possibility of pink circles / delamination. ‘

Akahoshi等氏之美國專利4,642，161號，Nakaso等氏之美國專利4,902,5 5 1號及Kajihara等氏之美國專利 4,98 1，560號及許多其中所引用之參考資料所提之製程，其包含電路內層之銅表面在將電路內層組裝成多層電路之前，均先經處理而在表面有接著促進用之氧化銅。然後利用特殊的還原劑及條件，使所形成的氧化銅還原成金屬銅。於是採用此種電路內層之多層複合材料，在其後的穿孔加工，局部露出內層的銅時因爲沒有氧化銅可供局部溶解，故不會形成粉紅圈。然而此類型之製程 538080 五、發明説明（4 ) 採用其他技術時，介電底層和金屬銅電路內層之間的接著性是存疑的。在還原製程中此現象特別明顯，因爲電路結合表面不僅是金屬銅，而且有不同”相，，的金屬銅：亦即（1 )氧化銅還原所得之銅及（2 )銅箔之銅，其在”相” 界處容易剝離/脫層。Akahoshi et al. US Patent No. 4,642,161, Nakaso et al. US Patent No. 4,902,5 51 and Kajihara et al. US Patent No. 4,98 1,560, and many of the processes cited in the references cited therein, The copper surface containing the inner layer of the circuit is processed before the inner layer of the circuit is assembled into a multilayer circuit, and then there is copper oxide on the surface for subsequent promotion. Then, using special reducing agents and conditions, the formed copper oxide is reduced to metallic copper. Therefore, when the multilayer composite material of the inner layer of such a circuit is used, the copper layer will not form a pink circle when there is no copper oxide available for partial dissolution when the inner layer of copper is partially exposed. However, this type of process is 538080. 5. Description of the Invention (4) When other technologies are used, the connection between the dielectric bottom layer and the inner layer of the metal copper circuit is questionable. This phenomenon is particularly obvious in the reduction process, because the circuit bonding surface is not only metallic copper, but also different "phases" of metallic copper: (1) copper obtained by reduction of copper oxide and (2) copper of copper foil, which Easily peeled / delaminated at the "phase" boundary.

Adler氏之美國專利4,997,722號及4,997,5 1 6號亦提出在電路內層之銅表面形成氧化銅，之後以特殊的還原溶液處理，將氧化銅還原成金屬銅。某些部分的氧化銅顯然地並不均還原成金屬銅，而是只還原到水合的氧化亞銅或氫氧化亞銅，此等亞銅其後會溶於非氧化性酸，而該酸並不侵犯或溶解已還原成金屬銅之部分◦於是採用此種電路內層之多層組合物因在其後的穿孔加工中並沒有氧化銅可供局部溶解及底層的銅的局部曝露，故不會產生粉紅圈。然而，未能解決的問題是介電層和金屬銅電路內層之間的接著性差，首先因爲粘合表面係金屬銅，其次因爲金屬銅主要是存在於不同的相：亦即（！）氧化銅還原而得之銅及（2)銅箔之銅，故沿著相界容易剝離/脫層。可參閱Ferrier等氏之美國專利5,2 8 9,6 3 0號，其發表的製程包含在電路元件上形成氧化銅接著促進層，然後做有控制的溶解，並移除實質量的氧化銅，但不妨害苴形能。U.S. Patent Nos. 4,997,722 and 4,997,5 1 6 of Adler's also propose to form copper oxide on the copper surface of the inner layer of the circuit, and then treat it with a special reducing solution to reduce the copper oxide to metallic copper. Obviously, some portions of copper oxide are not reduced uniformly to metallic copper, but only to hydrated cuprous oxide or cuprous hydroxide, which are then dissolved in non-oxidizing acids, which Does not infringe or dissolve the part that has been reduced to metallic copper. Therefore, the multilayer composition using the inner layer of this circuit will not be partially dissolved and the underlying copper is partially exposed in the subsequent perforation process. Generates pink circles. However, the problem that cannot be solved is the poor adhesion between the dielectric layer and the inner layer of the metal copper circuit, firstly because the bonding surface is metal copper, and secondly because metal copper mainly exists in different phases: that is, (!) Oxidation Copper obtained by reduction of copper and (2) copper of copper foil are easy to peel / delaminate along the phase boundary. See also US Patent No. 5,2 8 9,6 3 0 by Ferrier et al. The published process includes forming a copper oxide on a circuit element, then promoting a layer, then performing a controlled dissolution, and removing the actual mass of copper oxide. , But it does not hinder the shape energy.

McGrath氏之世界專利申請案WO 96/ 1 9097號提出聚合物材料對金屬表面之接著性改良法。此法乃使金屬表 -6- 538080 五、發明説明（5 ) 面接觸含有過氧化氫、無機酸、銹蝕抑制劑及季銨界面活性劑之接著促進組成物。McGrath's world patent application WO 96/119097 proposes a method for improving the adhesion of polymer materials to metal surfaces. This method is to make the metal surface -6- 538080. 5. Description of the invention (5) The surface is in contact with the composition containing hydrogen peroxide, inorganic acid, rust inhibitor and quaternary ammonium surfactant.

Ferrier氏之美國專利5,8 69，130號之製程係用含有氧化劑、酸、銹蝕抑制劑，鹵離子來源及任意之水溶性聚合物的組成物處理金屬表面，以提升聚合物材料對金屬表面之粘著性。本發明提出改善聚合物材料對金屬表面，尤其是銅或銅合金表面之粘著性的方法。本方法特別適用於多層印刷電路板之製備。和傳統之方法比較起來，本法可使金屬和聚合物表面（亦即電路及中間的絕緣層）之間有最適的接著性，可消除粉紅圈或使之最小化，並能經濟地操作。發明槪述本發明者提供聚合物材料對金屬表面，尤指銅及銅合金表面的接著性的改良法。本方法包含： 1)使金屬表面與粘著促進組成物接觸，其包含： a) 氧化劑； b) 酸； c) 銹蝕抑制劑； d) 在1-位置具有比氫更會吸電子之吸電子基的苯並***， e) 任意之粘著加強種類的來源，該加強種類選自鉬酸鹽，鎢酸鹽，鉅酸鹽，鈮酸鹽，釩酸鹽，鉬、鎢、鉅、鈮、釩之異多酸（i s ο ρ ο 1 y a c i d)或雜多 538080 五、發明説明（6 ) 酸（heteropoly acid)，以及任何前述加強種類； 2)其後使聚合物材料粘合在金屬表面上。本案發明者發現前述方法可改善金屬表面對聚合物材料之接者性’該金屬表面特別是銅或銅合金。本方法特別適合製造多層印刷電路板。發明之詳細說明亦即本案發明者發現金屬表面先接觸粘著促進組成物後，就可改善金屬表面和聚合物材料之間的粘著性。因此，本發明提供聚合物材料對金屬表面粘著性之改良法，包含： 1) 使金屬表面與粘著促進組成物接觸，其包含： a) 氧化劑； b) 酸； c) 銹蝕抑制劑； d) 較佳在1 -位置具比氫基更能吸電子之吸電子基的苯並***，該吸電子基較佳爲選自羥基，胺基，硝基，腈基，磺酸基，羧基，鹵基，锍基及未飽和之烴基；及 e) 任意之接著加強種類，選自鉬酸鹽，鎢酸鹽，鉅酸鹽，鈮酸鹽，釩酸鹽，鉬、鎢、鉅、鈮、釩之異多酸或雜多酸，以及前述之任何組合； 0任意之水溶性聚合物； g)較佳有鹵離子之來源；及 2) 然後使聚合物材料粘合在金屬表面。 538080 五、發明説明（7 ) 本發明者發現本粘著促進組成物可在金屬上產生粗糙的塗層表面。所得之表面特別適合粘著聚合物材料，因爲和未處理之金屬表面比較起來，粘著力顯著地增大。此外，經處理（塗佈）之金屬表面可長期的維持改良的粘著性，並可降低任何非所欲的金屬和聚合物材料之間的反應產生之可能性。本方法特別適用於多層印刷電路板之製造。於是在此應用中，內層之金屬電路（通常是銅）是以本粘著促進組成物處理。處理後，以水洗，內層以例如做爲預浸坯料之聚合物或可顯像之介電質粘合，即可得多層印刷電路板。欲處理之金屬表面可爲各種金屬，如銅、銅合金、鎳及鐵。但若金屬表面係銅或銅合金，則可得最佳效果。聚合物材料可爲各種聚合物，包含預浸坯料，可顯像介電質、光線形成性樹脂，焊罩，接著劑或聚合物蝕刻光阻劑。用於粘合促進組成物之氧化劑乃能使金屬表面氧化之任何氧化劑。本發明者發現過氧化氫及過硫酸鹽爲本發明方法中特佳之氧化劑，最好是過氧化氫。在接著促進組成物中之氧化劑濃度爲2至60克/升，較佳爲3至30克/升。用於接著促進組成物中之酸乃在基料中安定之任何酸，但本發明者發現較佳爲無機酸，特佳爲硫酸。在接著促進組成物酸之濃度爲5至3 6 0克/升，較佳爲2 0 538080 五、發明説明（8 ) 著促進組成物酸之濃度爲5至3 6 0克/升，較佳爲2 0 至1 10克/升。用於接著促進組成物中之銹蝕抑制劑乃能與金屬表面反應形成保護性錯合物層之化合物。較佳之銹蝕抑制劑選自***，苯並***，四唑，咪唑，苯並咪唑及前述之混合物。特佳爲苯並***。銹蝕抑制劑在接著促進組成物中之濃度爲0.2至20克/升，較佳爲1至12克/ 升。本發明者發現添加在位置有吸電子能力強過氫基之吸電子基的苯並***，則有利於形成均勻的塗層，且粘合後粘著力強。本發明者發現吸電子基較佳的選自羥基，胺基，硝基，腈基，磺酸基，羧基，鹵基，锍基及未飽和之院基。最好是吸電子基爲經基：，因此，最佳的材料爲1 -羥基苯並***：Ferrier's U.S. Patent No. 5,8,69,130 processes metal surfaces with a composition containing oxidants, acids, rust inhibitors, sources of halogen ions, and any water-soluble polymer to enhance the polymer material's effect on the metal surface. Adhesiveness. The present invention proposes a method for improving the adhesion of a polymer material to a metal surface, especially a copper or copper alloy surface. This method is particularly suitable for the preparation of multilayer printed circuit boards. Compared with the traditional method, this method can make the best adhesion between the metal and the polymer surface (that is, the circuit and the intermediate insulation layer), can eliminate or minimize the pink circle, and can operate economically. SUMMARY OF THE INVENTION The present inventors have provided a method for improving the adhesion of a polymer material to a metal surface, especially copper and copper alloy surfaces. The method includes: 1) contacting a metal surface with an adhesion promoting composition, comprising: a) an oxidant; b) an acid; c) a rust inhibitor; d) having an electron withdrawing electron at a 1-position more than hydrogen Benzotriazole, e) a source of any adhesion-enhancing species selected from molybdate, tungstate, giant, niobate, vanadate, molybdenum, tungsten, giant, niobium Vanadium isopolyacid (is ο ρ ο 1 yacid) or heteropoly 538080 5. Description of the invention (6) Heteropoly acid, and any of the aforementioned strengthening types; 2) The polymer material is then adhered to the metal surface on. The inventor of the present case found that the aforementioned method can improve the accessibility of a metal surface to a polymer material ', and the metal surface is particularly copper or a copper alloy. This method is particularly suitable for manufacturing multilayer printed circuit boards. Detailed description of the invention That is, the inventor of the present invention discovered that the adhesion between the metal surface and the polymer material can be improved after the metal surface first contacts the adhesion promotion composition. Therefore, the present invention provides a method for improving the adhesion of a polymer material to a metal surface, including: 1) contacting a metal surface with an adhesion promotion composition, which includes: a) an oxidant; b) an acid; c) a rust inhibitor; d) benzotriazole having an electron-withdrawing group which is more electron-withdrawing than a hydrogen group at the 1-position. Carboxyl, halo, fluorenyl, and unsaturated hydrocarbon groups; and e) any of the following reinforcing types selected from molybdate, tungstate, giant salt, niobate, vanadate, molybdenum, tungsten, giant, Heteropoly or heteropoly acids of niobium and vanadium, and any combination of the foregoing; 0 any water-soluble polymer; g) preferably a source of halide ions; and 2) the polymer material is then bonded to the metal surface. 538080 5. Description of the invention (7) The present inventors found that the adhesion promotion composition can produce a rough coating surface on a metal. The resulting surface is particularly suitable for adhering polymer materials, as the adhesion is significantly increased compared to untreated metal surfaces. In addition, the treated (coated) metal surface can maintain improved adhesion for a long period of time, and can reduce the possibility of any undesired reaction between the metal and the polymer material. This method is particularly suitable for the manufacture of multilayer printed circuit boards. Therefore, in this application, the inner metal circuit (usually copper) is treated with the adhesion promoting composition. After the treatment, it is washed with water, and the inner layer is bonded with, for example, a polymer as a prepreg or a developable dielectric, so that printed circuit boards can be printed in multiple layers. The metal surface to be treated can be various metals such as copper, copper alloy, nickel and iron. But if the metal surface is copper or copper alloy, the best results can be obtained. Polymer materials can be a variety of polymers, including prepregs, which can develop dielectrics, light-forming resins, solder masks, adhesives, or polymer etching photoresists. The oxidant used in the adhesion-promoting composition is any oxidant that can oxidize the metal surface. The inventors have found that hydrogen peroxide and persulfate are particularly preferred oxidants in the method of the invention, and hydrogen peroxide is the most preferred. The concentration of the oxidant in the subsequent promotion composition is 2 to 60 g / L, preferably 3 to 30 g / L. The acid used to subsequently promote the composition is any acid that is stable in the base material, but the inventors have found that inorganic acids are preferred, and sulfuric acid is particularly preferred. Next, the concentration of the acid in the promoting composition is 5 to 360 g / l, preferably 20 538080. 5. Description of the invention (8) The concentration of the acid in the promoting composition is 5 to 360 g / l, preferably For 20 to 1 10 g / l. The rust inhibitor used in the subsequent promotion of the composition is a compound capable of reacting with the metal surface to form a protective complex layer. Preferred rust inhibitors are selected from triazole, benzotriazole, tetrazole, imidazole, benzimidazole and mixtures of the foregoing. Particularly preferred is benzotriazole. The concentration of the rust inhibitor in the subsequent promotion composition is 0.2 to 20 g / l, preferably 1 to 12 g / l. The inventors have found that the addition of a benzotriazole having an electron-withdrawing group having a strong hydrogen-withdrawing group at the position is beneficial to the formation of a uniform coating and has strong adhesion after bonding. The present inventors have found that the electron-withdrawing group is preferably selected from the group consisting of a hydroxy group, an amine group, a nitro group, a nitrile group, a sulfonic acid group, a carboxyl group, a halogen group, a fluorenyl group, and an unsaturated group. It is preferred that the electron withdrawing group is a meridian group: Therefore, the best material is 1-hydroxybenzotriazole:

銹蝕抑制劑及1 _位置具吸電子基之苯並***可爲同一化合物。例如1 _羥基苯並***本身就可扮演此兩角 -10- 538080 五、發明説明（9 ) 色。若再添加下列之接著加強種類配合接著促進組成物中之前述材料，則效果更是突出。本發明者發現如此組合可產生綜效。在1-位置有吸電子基之苯並***濃度可爲0.2至20克/升，較佳爲0.5至5克/升。接著加強種類之來源可爲能提供接著加強種類之任何材料，選自鉬酸鹽、鎢酸鹽、鉅酸鹽、鈮酸鹽、釩酸鹽及其混合物；例如鹼金屬之鉬酸鹽、鎢酸鹽、鉅酸鹽、鈮酸鹽、釩酸鹽及其混合物，如鉬酸、鎢酸或釩酸之鈉（或鉀）鹽，以及鉬、鎢、鉬、鈮或釩之雜多酸或異多酸。於是鉬酸鹽或鎢酸鹽可包含雜原子，如磷、矽、鈷、猛及鎢。較佳爲來源爲鉬、鎢、鈮、釩及其混合物之異多酸及雜多酸，如鉬酸，釩酸及鎢酸，最好的接著加強種類爲鉬酸。接著加強種類在接著促進組成物中之濃度爲1毫克/升至500毫克/升（端賴於接著促進離子含量而定）’較佳爲5毫克/升至200毫克/升。接著加強種類可配用或不配用1 -位置具吸電子基之苯並三口坐〇接著促進組成物中亦可任意含有水溶性聚合物。若有用，則水溶性聚合物較佳爲不是潤淫劑或界面活性劑，而是低分子量水溶性單體聚合而得之水溶性均聚物或共聚物。最好是水溶性聚合物爲環氧乙烷之聚合物，聚乙二醇，聚丙二醇或聚乙烯醇。最好是環氧乙烷聚合物，或聚乙二醇（聯碳公司之Carbowax®)。本發明者發現 -11- 538080 五、發明説明（1G )The rust inhibitor and the benzotriazole having an electron withdrawing group at the 1-position may be the same compound. For example, 1-hydroxybenzotriazole itself can play these two corners -10- 538080 5. Invention description (9) color. If the following materials are further added to strengthen the composition and then promote the composition, the effect is even more prominent. The inventors have found that such a combination produces synergistic effects. The concentration of benzotriazole having an electron withdrawing group at the 1-position may be 0.2 to 20 g / l, preferably 0.5 to 5 g / l. The source of the next strengthening species may be any material that provides the next strengthening species, selected from molybdates, tungstates, giants, niobates, vanadates, and mixtures thereof; for example, molybdates, tungstens of alkali metals Acid salts, giant salts, niobates, vanadates and mixtures thereof such as sodium (or potassium) salts of molybdic acid, tungstic acid or vanadate, and heteropoly acids of molybdenum, tungsten, molybdenum, niobium or vanadium or Isopoly acid. So molybdate or tungstate can contain heteroatoms such as phosphorus, silicon, cobalt, tungsten and tungsten. Heteropoly acids and heteropoly acids, such as molybdic acid, vanadic acid and tungstic acid, which are preferably derived from molybdenum, tungsten, niobium, vanadium, and mixtures thereof, are most preferably the next enhanced type is molybdic acid. The concentration of the next-strengthening species in the next-promoting composition is 1 mg / l to 500 mg / l (depending on the content of the next-promoting ion) ', preferably 5 mg / l to 200 mg / l. Next, the type of reinforcement can be used with or without the 1-position benzotrisine with an electron-withdrawing group. Next, the composition can optionally contain a water-soluble polymer. If it is useful, the water-soluble polymer is preferably a water-soluble homopolymer or copolymer obtained by polymerizing a low-molecular-weight water-soluble monomer instead of an emotive or surfactant. Most preferably, the water-soluble polymer is a polymer of ethylene oxide, polyethylene glycol, polypropylene glycol or polyvinyl alcohol. Preferred is ethylene oxide polymer, or polyethylene glycol (Carbowax® of Union Carbon). The inventors found -11- 538080 V. Description of the invention (1G)

Carbowax 750 及 Carbowax MPEG 2000 特別有用。亦特別有用的是B ASF公司之環氧乙烷均聚物（Pluronic®)。在接著促進組成物中水溶性聚合物之濃度爲1至1 5克/ 升，較佳爲3至6克/升。於是接著促進組成物必須含有酸，氧化劑及銹蝕抑制劑。較佳爲組成物亦含有本文中所述在Μ立置具吸電子基之苯並***，或是銹触抑制劑本身就是在1 -位置具吸電子基之苯並***。在另一場合下，組成物較佳爲亦含有本文中所述之粘著加強種類，而在1 -位置具吸電子基之苯並***可用亦可不用。較佳爲接著促進組成物亦含有鹵離子來源，其乃在接著促進組成物之基料中可提供鹵離子之化合物。較佳爲鹵離子來源爲鹼金屬鹽，如氯化鈉或氯化鉀，氧鹵化物，如氯酸鈉或氯酸鉀，或帶鹵之無機酸，如氫氯酸。較佳爲鹵離子來源可對接著促進組成物提供氯離子，最好是提供氯酸離子。在接著促進組成物中鹵離子之來源的濃度爲5至500毫克/升，較佳爲10至50毫克/升 (對鹵離子重量而言）。接著促進組成物可依各種方法（包含浸漬，噴洒或溢流）處理金屬表面。在處理時，接著促進組成物之溫度爲80°F至150°F，較佳爲90°F至120°F。處理時間可爲 1 5秒至1 5分鐘，較佳爲1至2分鐘，端賴處理之溫度及方法而定。茲以非限制範圍之實施說明。 -12- 538080 五、發明説明（11 ) 實例中用來加工銅鍍板及銅箔之週期如下：時間（分鐘） 5%硫酸，70°F 1 冷水洗 1 泡銅淸潔齊!）（Metex Brass Soak Cleaner S-426，150°F) 2 冷水洗 2 預浸（2克苯並***/升，1% v/v 50%H202)，70°F 1Carbowax 750 and Carbowax MPEG 2000 are particularly useful. Also particularly useful is B ASF's ethylene oxide homopolymer (Pluronic®). The concentration of the water-soluble polymer in the subsequent promotion composition is 1 to 15 g / l, preferably 3 to 6 g / l. Then the promoting composition must contain acids, oxidants and rust inhibitors. It is preferred that the composition also contains a benzotriazole having an electron-withdrawing group as described herein, or that the rust inhibitor itself is a benzotriazole having an electron-withdrawing group at the 1-position. In another case, the composition preferably also contains the adhesion-enhancing species described herein, and benzotriazole having an electron-withdrawing group at the 1-position may be used or not. It is preferred that the subsequent promotion composition also contains a halide ion source, which is a compound that can provide a halide ion in the base of the subsequent promotion composition. Preferably, the halide ion source is an alkali metal salt, such as sodium or potassium chloride, an oxyhalide, such as sodium or potassium chlorate, or a halogenated inorganic acid, such as hydrochloric acid. Preferably, the halide ion source provides chloride ions to the subsequent promotion composition, and most preferably provides chlorate ions. The concentration of the source of halide ions in the subsequent promotion composition is 5 to 500 mg / liter, preferably 10 to 50 mg / liter (for the weight of the halide ion). The promoting composition can then treat the metal surface in a variety of ways, including dipping, spraying, or overflowing. At the time of treatment, the temperature of the promoting composition is then 80 ° F to 150 ° F, preferably 90 ° F to 120 ° F. The processing time may be 15 seconds to 15 minutes, preferably 1 to 2 minutes, depending on the processing temperature and method. This is a non-limiting implementation note. -12- 538080 V. Description of the Invention (11) The cycle used to process copper plate and copper foil in the example is as follows: Time (minutes) 5% sulfuric acid, 70 ° F 1 cold water wash 1 copper foam clean!) (Metex Brass Soak Cleaner S-426, 150 ° F) 2 cold water wash 2 prepreg (2 g benzotriazole / liter, 1% v / v 50% H202), 70 ° F 1

試驗溶液 1 冷水洗 1 強風吹乾 1 窨例1-15Test solution 1 Wash with cold water 1 Dry with strong wind 1 Example 1-15

製備基礎之接著促進溶液，其中含2體積％硫酸（9 8 重量％濃度），〇·75體積％過氧化氫（50重量％濃度），4 克苯並***/升，其餘爲水。每一例中，於前述之基礎溶液中加入下列表1所示用量的羥基苯並***水合物及銦酸，並依前述標準週期以特定之溶液處理銅箔及鍍銅板，處理溫度如表中所示。表1亦列出所得試樣之外觀。 -13- 538080 五、發明説明（12 )The basis was then prepared to promote a solution containing 2 vol% sulfuric acid (98% by weight), 0.75 vol% hydrogen peroxide (50% by weight), 4 g of benzotriazole / liter, and the remainder being water. In each case, hydroxybenzotriazole hydrate and indium acid in the amounts shown in Table 1 below were added to the aforementioned base solution, and the copper foil and copper plate were treated with the specific solution according to the aforementioned standard cycle. The processing temperature is as shown in the table. As shown. Table 1 also lists the appearance of the obtained samples. -13- 538080 V. Description of the invention (12)

表I 例 1-羥基苯並 ***水合物 (克/升）鉬酸 (毫克/升）溫度 (T ) 外觀 —.—--- 1 〇克/升〇毫克/升 1 00T 不均勻之暗粉紅色 2 1克/升〇毫克/升 1 00°F 不均勻之暗粉紅色 3 2克/升〇毫克/升 1 00°F 均勻暗粉紅色 4 3克/升〇毫克/升 1 00°F 均勻暗粉紅色 5 3克/升〇毫克/升 1 1 0°F 均勻很暗之粉紅色 6 3克/升〇毫克/升 1 20°F 均勻暗粉紅色 7 3克/升 10毫克/升 1 00°F 不均句日首褐色 8 3克/升 10毫克/升 1 1 0°F 均勻很暗之褐色 9 3克/升 10毫克/升 1 20°F 均勻暗褐色 10 3克/升 20毫克/升 100°F 均勻很暗之褐色 11 3克/升 20毫克/升 1 1 0°F 均勻暗褐色 12 3克/升 20毫克/升 1 2 0°F 均勻暗褐色 13 3克/升 30毫克/升 1 00°F 均勻褐色 14 3克/升 30毫克/升 1 1 0°F 均勻暗褐色 15 3克/升 30毫克/升 1 20°F 均勻很暗之褐色加工後，板及箔在23 0 °F烤30分鐘，然後壓塑機 (NELCO 公司之 NELCO N4205-2B FR-4)在 350 T 及 200 磅/吋2之壓力層合。壓塑機包含兩片1〇80玻璃包夾一片762 8玻璃。層合後，照像使板形成1吋寬之條紋，並除去過量的銅。使條紋板在23 0°F烤2小時，然後浸入5 5 0 °F焊劑中〇、1 0及2 0秒將箔條自樹脂剝離’ 測定銅對樹脂之粘合力，結果列於下列表11中。 538080 五、發明説明（13 ) 表u 例外觀焊接後外觀剝離強度 (0秒焊接）剝離強度 (10秒焊接) 剝離強度 (20秒焊接） 1 不均勻暗粉紅色不均勻暗粉紅色 3.5磅/吋 3.2磅/吋 3·8磅/吋 2 不均勻非常暗粉紅色不均勻很暗之粉紅色 4·2磅/吋 3.8磅/吋 3.8磅/吋 3 均勻褐/粉紅色均勻褐/粉紅色 4.8磅/吋 4.5磅/吋 4.2磅/吋 4 均勻褐/粉紅色均勻褐/粉紅色 5.5石旁/吋 5·〇磅/吋 5.0磅/吋 5 均勻暗褐色均勻暗褐色 6.0磅/吋 4.8磅/吋 Ϊ.8 磅 6 均勻暗褐色暗褐色 3.0磅/吋 2.0磅/吋 1.8磅/吋— 7 均勻暗褐色均勻暗褐色 5.2石芳/时 4.8磅/吋 4.8磅/吋~ 8 均勻紫/褐色均勻紫/褐色 6.2膀/吋 5.5磅/吋 5.2磅/吋— 9 均勻紫/褐色均勻紫/褐色 6.2磅/吋 5·8磅/吋 5.0磅/吋— 10 均勻紫/褐色均勻紫/褐色 5.5石旁/吋 5.0磅/吋 4.8磅/吋— 11 均勻紫/褐色均勻紫/褐色 5.8磅/吋 5.2磅/吋 5.2磅/吋— 12 均勻紫/褐色均勻紫/褐色 1.0磅/吋 5.2磅/吋 4.8膀/吋— 13 均勻紫/褐色均勻紫/褐色 5.5磅/吋 5.0磅/吋 4.8磅/吋 14 均勻紫/褐色均勻紫/褐色 5.5磅/吋 5.0磅/吋 5.0磅/吋 15 均勻紫/褐色均勻紫/褐色 5.5磅/吋 5·〇膀/吋 4.2磅/吋由此等例子可看出本發明方法在外觀及粘著力均優異。實例16 重覆實例1，但試驗溶液中苯並***之濃度由4克/ 升提到7克/升。如實例1，1 -羥基苯並***或鉬酸均不用。結果得均勻粉紅色外觀。在5 5 0 °F焊接之剝離強度分別爲2 _ 8磅/吋（0秒），2.5 5芳/吋（1 0秒）及2.5磅/ 吋（2 0秒）。 -15- 538080 五 '發明説明（14 ) 實例1 7 加熱含有下列成分之銅處理溶液至約95 °F : 4.6體積 %硫酸，2.8體積％過氧化氫（50重量％濃度），6.3克/ 升之苯並***，約1 5毫克/升之氯化鈉，約1克/升之聚環氧乙烷（Carbo wax MPEG 2000)及21.6克/升之銅離子（爲活化已老化或用過之接著促進組成物，例如當接著促進組成物用於銅表面，就在溶於中建立銅離子 )。製備含有2克/升苯並***及2體積％過氧化氫（5 0 重量％濃度）之新鮮的預浸溶液。稱塗樹脂之銅板（1.5 吋寬x3吋高）之重量，並按下列週期進行處理：酸洗齊!l(Metex 927 1 *，10%，125°F) 2分鐘冷水洗 2分鐘預浸，室溫 1分鐘銅處理溶液，9 5 °F 1分鐘冷水洗 1分鐘強風乾燥 1分鐘註：*康乃狄克州Water bury地之MacDer mid公司出品。經處理後，板有紫/銹色表面外觀。稱取板重，由減少之重量可計算出自表面移除之銅的大約厚度。利用相同週期處理1盎斯的塗樹脂銅板及銅箔。然後在銅處理溶液中加入5 0毫克/升的鉬酸，並重覆此實驗。又加入5 0毫克/升的鉬酸，每次添加後，又做實驗，直到全部加入量爲150毫克/升。利用Nelco 4205-2玻璃/ -16- 538080 五 '發明説明（) 运氧壓塑機將配合之芯層及箔層合在一起。層合後，將板飽刻成箔面有1吋寬的條紋，烘烤並浸入5 5 0卞錫/ 錯焊劑中〇，丨〇及2〇秒。浸焊劑後，對每一板測試剝離強度。結果如下：實驗蝕刻 0秒焊接 1 0秒焊接 20秒焊接〇毫克/升之鉬酸 65微吋 3·2磅/吋 3.2磅/吋 2.0磅/吋 50毫克/升之鉬酸 70微吋 4.2磅/吋 4.2磅/吋 3.5磅/吋 1〇〇毫克/升之鉬酸 65微吋 4.8磅/吋 4.5磅/吋 4.0磅/吋 150毫克/升之鉬酸 65微吋 5.0磅/吋 4.8磅/吋 4.8磅/吋在此系統中提高鉬酸濃度，則在未用焊劑及焊劑應力條件下，均會明顯提升銅/樹脂之剝離強度。實例1 8Table I Example 1-Hydroxybenzotriazole hydrate (g / l) Molybdic acid (mg / l) Temperature (T) Appearance --- ----10 g / l 0 mg / l 100T uneven dark Pink 2 1 g / l 0 mg / l 100 ° F Uneven dark pink 3 2 g / l 0 mg / l 100 ° F Even dark pink 4 3 g / l 0 mg / l 100 ° F Even dark pink 5 3 g / l 0 mg / l 1 1 0 ° F Even dark pink 6 6 g / l 0 mg / l 1 20 ° F Even dark pink 7 3 g / l 10 mg / Liter 100 ° F Uneven sentence First brown 8 3 g / l 10 mg / l 1 1 0 ° F Even dark brown 9 3 g / l 10 mg / l 1 20 ° F Dark brown 10 3 g / Liter 20 mg / liter 100 ° F Even dark brown 11 3 g / liter 20 mg / liter 1 1 0 ° F Even dark brown 12 3 g / liter 20 mg / liter 1 2 0 ° F Even dark brown 13 3 g / L 30mg / L 1 00 ° F Even brown 14 3 g / L 30mg / L 1 1 0 ° F Even dark brown 15 3g / L 30mg / L 1 20 ° F After processing even dark brown Plates and foils are baked at 230 ° F for 30 minutes, then a compression molding machine (NELCO N42 by NELCO Corporation) 05-2B FR-4) Laminated at 350 T and 200 psi. The compression molding machine consists of two 1080 glass envelopes and one 76 28 glass. After lamination, the board was photographed to form a 1-inch wide stripe and excess copper was removed. Bake the stripe board at 23 0 ° F for 2 hours, then immerse it in the flux at 550 ° F for 0, 10, and 20 seconds to peel the foil from the resin. The copper adhesion to the resin was measured. The results are listed in the following table. 11 in. 538080 5. Description of the invention (13) Table u Example appearance Appearance peel strength after welding (0 second welding) Peel strength (10 second welding) Peel strength (20 second welding) 1 Uneven dark pink Uneven dark pink 3.5 lbs / Inch 3.2 lbs / inch 3. 8 lbs / inch 2 Uneven very dark pink Uneven very dark pink 4.2 lbs / inch 3.8 lbs / inch 3.8 lbs / inch 3 Even brown / pink Even brown / pink 4.8 lbs / inch 4.5 lbs / inch 4.2 lbs / inch 4 Uniform Brown / Pink Uniform Brown / Pink 5.5 Next to Stone / inch 5.0 lb / inch 5.0 lb / inch 5 Uniform Dark Brown Uniform Dark Brown 6.0 lb / inch 4.8 Pounds / inches. 8 pounds 6 Even dark brown Dark brown 3.0 pounds / inch 2.0 pounds / inch 1.8 pounds / inch — 7 Even dark brown Even dark brown 5.2 Shifang / hour 4.8 pounds / inch 4.8 pounds / inch ~ 8 Even purple / Brown uniform purple / brown 6.2 b / inch 5.5 lb / inch 5.2 lb / inch — 9 even purple / brown uniform purple / brown 6.2 lb / inch 5.8 lb / inch 5.0 lb / inch — 10 even purple / brown uniform purple / Brown 5.5 stone side / inch 5.0 lb / inch 4.8 lb / inch — 11 even purple / brown uniform purple / brown 5.8 lb / inch 5.2 lb / inch 5.2 lb / inch — 12 even purple / Uniform purple / brown 1.0 lb / inch 5.2 lb / inch 4.8 b / inch — 13 Uniform purple / brown Uniform purple / brown 5.5 lb / inch 5.0 lb / inch 4.8 lb / inch 14 Uniform purple / brown Uniform purple / brown 5.5 lb 5.0 lbs / inch 5.0 lbs / inch 15 Uniform purple / brown Uniform purple / brown 5.5 lbs / inch 5.0 mm / inch 4.2 lb / inch From these examples, it can be seen that the method of the present invention is excellent in appearance and adhesion . Example 16 Example 1 was repeated, but the concentration of benzotriazole in the test solution was changed from 4 g / l to 7 g / l. As in Example 1, neither 1-hydroxybenzotriazole or molybdic acid was used. The result is a uniform pink appearance. The peel strengths at 5 50 ° F were 2 -8 lbs / inch (0 seconds), 2.5 5 ar / inch (10 seconds), and 2.5 lb / inch (20 seconds). -15- 538080 Five 'Invention Description (14) Example 1 7 Heat a copper treatment solution containing the following ingredients to about 95 ° F: 4.6 vol% sulfuric acid, 2.8 vol% hydrogen peroxide (50% by weight), 6.3 g / l Benzotriazole, about 15 mg / L of sodium chloride, about 1 g / L of polyethylene oxide (Carbo wax MPEG 2000) and 21.6 g / L of copper ions (aged or used for activation) The composition is then promoted, such as when the composition is subsequently applied to a copper surface, copper ions are created in solution). A fresh prepreg solution containing 2 g / L benzotriazole and 2 vol% hydrogen peroxide (50% by weight concentration) was prepared. Weigh the resin-coated copper plate (1.5 inches wide x 3 inches high) and process them according to the following cycle: Pickled! L (Metex 927 1 *, 10%, 125 ° F) 2 minutes cold water wash 2 minutes pre-immersion, Copper treatment solution for 1 minute at room temperature, 95 ° F for 1 minute, cold water wash for 1 minute, strong air drying for 1 minute Note: * Manufactured by MacDer mid, Waterbury, Connecticut. After treatment, the board has a purple / rusty surface appearance. Weigh the board and calculate the approximate thickness of copper removed from the surface from the reduced weight. Use the same cycle to process 1 oz of resin-coated copper plate and copper foil. 50 mg / L molybdic acid was then added to the copper treatment solution and the experiment was repeated. Add another 50 mg / L of molybdic acid. After each addition, experiment again until the total amount is 150 mg / L. Using Nelco 4205-2 glass / -16- 538080 5 'Invention description () Oxygen transport compression molding machine will combine the core layer and foil layer together. After lamination, the board was fully engraved to have a 1-inch wide stripe on the foil surface, baked and immersed in 550 tin / missoldering flux for 0, 0, and 20 seconds. After soldering, each board was tested for peel strength. The results are as follows: Experimental etching 0 seconds welding 10 seconds welding 20 seconds welding 0 mg / L molybdic acid 65 micro inches 3.2 pounds / inch 3.2 lbs / inch 2.0 pounds / inch 50 mg / liter molybdic acid 70 micro inches 4.2 4.2 lbs / inch 3.5 lbs / inch 100 mg / l molybdic acid 65 micro inches 4.8 lbs / inch 4.5 lbs / inch 4.0 lbs / inch 150 mg / l molybdic acid 65 micro inches 5.0 lbs / inch 4.8 4.8 lbs / inch In this system, increasing the concentration of molybdic acid will significantly increase the copper / resin peel strength without using flux and flux stress. Example 1 8

製備組成如下之銅處理溶液：約3體積％硫酸，0.75 體積％過氧化氫（50重量％濃度），8克/升苯並***及 3 〇毫克/升氯酸鉀。另製備含2克/升苯並***及1 體積％過氫化氫（5 0重量％濃度）之預浸液。依實例1之週期處理芯層及銅箔，並以本處理浴及預浸液代替實例 1之處理浴及預浸液。處理浴之溫度約1 0 0卞。然後在處理浴中添加1 0毫克/升之鉬酸’重覆實驗。處理後，仿實例1將芯層和銅箔層合’餓刻，烘烤並浸入焊劑中。結果如下： Λ1- 538080 五發明説明（μ )A copper treatment solution having the following composition was prepared: about 3 vol% sulfuric acid, 0.75 vol% hydrogen peroxide (50% by weight), 8 g / L benzotriazole and 30 mg / L potassium chlorate. A prepreg containing 2 g / L of benzotriazole and 1% by volume of hydrogen peroxide (50% by weight) was prepared. The core layer and the copper foil were processed according to the cycle of Example 1, and the processing bath and the prepreg were replaced by the processing bath and the prepreg. The temperature of the treatment bath is about 100 ° F. The experiment was then repeated by adding 10 mg / L of molybdic acid 'to the treatment bath. After the treatment, the core layer and the copper foil were laminated and patterned as in Example 1, baked, and dipped in solder. The results are as follows: Λ1- 538080 5. Description of the invention (μ)

實驗蝕刻 ~——-—_ 0秒焊接 "*----_____ 10秒焊接 ^^ 2〇秒焊接〇毫克/升鉬酸，l〇〇°F 20微吋 4·0碌/吋 3.8磅/吋 / τ J又 1〇毫克/升鉬酸，l〇〇°F 18微吋 5·2磅/吋 4.5磅/吋〇毫克/升鉬酸，ll〇°F 25微吋 4·8磅7吋 4.5磅/吋 3·〇 ΐ旁/吋 10毫克/升鉬酸，110°F 25微吋 5·8磅/吋 4.5磅/吋 3.5磅/吋 0毫克/升鉬酸，120°F 25微吋 5.5磅/吋 4.2磅/吋 3.2膀/时 10毫克/升鉬酸，120°F 25微吋 6.2磅/吋 5.2磅/吋 3.2磅/吋Experimental etching ~ ——-—_ 0 seconds welding " * ----_____ 10 seconds welding ^^ 20 seconds welding 0 mg / l molybdic acid, 100 ° F 20 micro inches 4.0 lumps / inch 3.8 Lbs / inch / τ J and 10 mg / l molybdic acid, 100 ° F 18 microinches 5.2 lbs / inch 4.5 lbs / inch molybdic acid, 110 ° F 25 microinches 4.8 7 inches 4.5 pounds per inch 3.0 mg / l molybdic acid, 110 ° F 25 micro inches 5.8 lbs / inch 4.5 lbs / inch 3.5 lbs / inch 0 mg / l molybdic acid, 120 ° F 25 microinches 5.5 lbs / inch 4.2 lbs / inch 3.2 mg / h 10 mg / l molybdic acid, 120 ° F 25 microinches 6.2 lbs / inch 5.2 lbs / inch 3.2 lbs / inch

由上表又淸楚地看出在銅處理液中加入鉬酸可改善銅對樹脂之粘著力。It is clear from the above table that adding molybdic acid to the copper treatment solution can improve the adhesion of copper to the resin.

-18--18-

Claims

538080 六、申請專利範圍第90 1 1 9979號「提昇聚合材料黏附金屬表面之方法及其所使用之組成物」專利案 (9 2年1月修正）申請專利範圍： 1. 一種提升聚合材料黏附金屬表面之方法，其中金屬表面包含銅，該方法包含： a)使金屬表面與接著促進組成物接觸，其包含： 1. 2至60克/升之過氧化氫； 2. 5至3 6 0克/升之硫酸； 3· 0 · 2至20克/升之銹蝕抑制劑，其選自***' 苯並***、咪唑、苯並咪唑、四唑及其混合物 4. 在1 -位置具吸電子基的苯並***，其吸電子基之吸電子能力大於氫基，及 5. 任意之接著加強種類之來源，該加強種類選自鉬酸鹽、鎢酸鹽、鉅酸鹽、鈮酸鹽、釩酸鹽，銷、鶴、組、銅、飢之異多酸或雑多酸’及任何前述之組合； b )使聚合物材料和金屬表面粘合。 2. 如申請專利範圍第1項之方法，其中銹蝕抑制劑係苯並三π坐。 3. 如申請專利範圍第1項之方法，其中吸電子基選自羥基、胺基、硝基、腈基、磺酸基、羧基、鹵基、 538080 六、申請專利範圍锍基及不飽和之烷基。 4. 如申請專利範圍第1項之方法’其中接著加強種類包含鉬酸離子。 5. 如申請專利範圍第1項之方法’其中在1 -位置具吸電子基之苯並***乃結構式如下之1 -羥基苯並***538080 VI. Application for Patent Scope No. 90 1 1 9979 "Method for Promoting the Adhesion of Polymeric Materials to Metal Surfaces and the Compositions Used Thereof" (Amended in January 1992) Scope of Patent Application: 1. A method for improving the adhesion of polymeric materials A method of a metal surface, wherein the metal surface comprises copper, the method comprising: a) bringing the metal surface into contact with an advancing composition comprising: 1.2 to 60 g / L of hydrogen peroxide; 2.5 to 3 6 0 G / l of sulfuric acid; 3.0 · 2 to 20 g / l of rust inhibitor selected from the group consisting of triazole 'benzotriazole, imidazole, benzimidazole, tetrazole and mixtures thereof. 4. 1-position with Electron-withdrawing benzotriazole, the electron-withdrawing ability of the electron-withdrawing group is greater than that of the hydrogen-based group, and 5. any of the sources of the subsequent strengthening type selected from the group consisting of molybdate, tungstate, giant salt, niobium Acid salts, vanadates, pins, cranes, groups, copper, isopolyacids or polyacids' and any combination thereof; b) bonding the polymer material to the metal surface. 2. The method according to item 1 of the scope of patent application, wherein the rust inhibitor is benzotriπ. 3. The method according to item 1 of the patent application, wherein the electron withdrawing group is selected from the group consisting of hydroxyl, amine, nitro, nitrile, sulfonic acid, carboxyl, halo, 538080. alkyl. 4. The method according to item 1 of the scope of patent application, wherein the next enhanced species includes molybdate ions. 5. The method according to item 1 of the scope of patent application, wherein the benzotriazole having an electron withdrawing group at the 1-position is a 1-hydroxybenzotriazole having a structural formula as follows

N 6. 如申請專利範圍第1項之方法，其中組成物包含鹵離子來源。 7. 如申請專利範圍第1項之方法，其中過氧化氫濃度爲3至30克/升。 8. 如申請專利範圍第7項之方法，其具有接著加強種類，且包含鉬酸離子。 9. 如申請專利範圍第 8項之方法，其銹蝕抑制劑選自三tl坐，苯並三卩坐，咪Π坐，四唑，苯並咪卩坐及其混合物。 10. 如申請專利範圍第 1項之方法，其中無機酸濃度爲 20至1 10克/ 升。 11. 一種組成物，其在金屬表面粘合聚合物材料之前’ 用以處理金屬表面，該組成物包含： 538080 t、申請專利範圍 a. 2至60克/升之過氧化氫； b. 5至3 60克/升之硫酸； c. 銹鈾抑制劑，其選自***、苯並***、咪唑、四唑、苯並咪唑及其混合物； d. 在1-位置具吸電子基的苯並***，其吸電子基之吸電子能力強於氫基，及 e. 任意之接著加強種類來源，該加強種類選自鉬酸鹽、鎢酸鹽、鉅酸鹽、鈮酸鹽、釩酸鹽，鉬、鎢、鉅、鈮、釩之異多酸或雜多酸，及其混合物。 1Z如申請專利範圍第 1 1項之組成物，其中過氧化氫濃度爲3至30克/升。 ia如申請專利範圍第 11項之組成物，其中吸電子基選自羥基、胺基、硝基、腈基、磺基、羧基、鹵基、锍基及不飽和烴基。 14. 如申請專利範圍第 1 1項之組成物，其中具有接著加強種類，且包含鉬酸離子。 15. 如申請專利範圍第 1 1項之組成物，其中吸電子基之苯並***乃下式所示之1-羥基苯並***：N 6. The method of claim 1, wherein the composition comprises a source of halide ions. 7. The method according to item 1 of the patent application range, wherein the hydrogen peroxide concentration is 3 to 30 g / l. 8. The method according to item 7 of the patent application, which has a subsequent strengthening type and contains molybdate ions. 9. The method of claim 8 in which the rust inhibitor is selected from the group consisting of tri-titanium, benzotripyridine, imidazole, tetrazole, benzimidazole, and mixtures thereof. 10. The method according to item 1 of the patent application range, wherein the concentration of the inorganic acid is 20 to 110 g / l. 11. A composition which is used to treat a metal surface before the polymer material is adhered to the metal surface, the composition comprising: 538080 t, patent application range a. 2 to 60 g / L of hydrogen peroxide; b. 5 To 3 60 g / L of sulfuric acid; c. Rust uranium inhibitor selected from triazole, benzotriazole, imidazole, tetrazole, benzimidazole and mixtures thereof; d. Electron-withdrawing group at 1-position Benzotriazole, whose electron-withdrawing ability is stronger than hydrogen-based, and e. Any subsequent reinforcement source, selected from molybdate, tungstate, giant salt, niobate, vanadium Acid salts, heteropoly acids or heteropoly acids of molybdenum, tungsten, macro, niobium, vanadium, and mixtures thereof. 1Z The composition according to item 11 of the patent application scope, wherein the hydrogen peroxide concentration is 3 to 30 g / l. ia The composition according to item 11 of the application, wherein the electron withdrawing group is selected from the group consisting of hydroxyl, amine, nitro, nitrile, sulfo, carboxyl, halo, fluorenyl, and unsaturated hydrocarbon. 14. The composition according to item 11 of the scope of patent application, which has a reinforced type and contains molybdate ions. 15. The composition according to item 11 of the scope of patent application, wherein the electron-withdrawing benzotriazole is a 1-hydroxybenzotriazole represented by the following formula:

538080 六、申請專利範圍〇 16. 如申請專利範圍第 1 1項之組成物，其中包含鹵離子來源。 17. —種組成物，其在聚合物材料粘合在金屬表面之前，用以處理金屬表面，該組成物包含： a. 2至60克/升過氧化氫； b . 5至3 6 0克/ 升硫酸； c. 1 -羥基苯並***； d .任意之接著加強種類之來源，該加強種類選自鉬酸鹽、鎢酸鹽、鉬酸鹽、鈮酸鹽、釩酸鹽，鉬、鎢、鉅、鈮、釩之異多酸或雜多酸，及其混合物〇 18. 如申請專利範圍第1 7項之組成物，其中尙包含羥基苯並***以外的銹蝕抑制劑。 19. 如申請專利範圍第 1 8項之組成物，其中錄蝕抑制劑選自***、苯並***、咪唑、苯並咪唑、四p坐及其混合物。 20·如申請專利範圍第 1 7項之組成物，其中具有接著加強種類，且包含鉬酸離子。 21·如申請專利範圍第 1 7項之組成物，其中過氧化氯之濃度爲3至30克/升。 22. —種組成物，其在聚合物材料粘合金屬表面之前，用以處理金屬表面，該組成物包含： 538080 六、申請專利範圍 a . 2至60克/升之過氧化氫； b· 5至3 60克/升之硫酸； c.在1-位置具有吸電子基的苯並***，其吸電子基之吸電子能力強於氫基。 23. 如申請專利範圍第 22項之組成物，其中吸電子基選自羥基、胺基、硝基、磺酸基、羧基、鹵基、毓基及不飽和烴基。 24. 如申請專利範圍第 22項之組成物，其中苯並*** 爲1 -羥基苯並***。 25. —種提升聚合材料黏附含銅金屬表面之方法，包含 a )使金屬表面與接著促進組成物接觸，其包含： 1. 2至60克/升過氧化氫； 2. 5至360克/升硫酸； 3·在1 -位置具吸電子基的苯並***，其吸電子基之吸電子能力大於氫基， b )使聚合物材料粘合在金屬表面。 26如申請專利範圍第25項之方法，其中吸電子基選自羥基、胺基、硝基、磺酸基、羧基、鹵基、锍基及不飽和烴基。 27.如申請專利範圍第2 5項之方法，其中苯並***係 1 -經基苯並三D坐。 28· —種組成物，其在聚合物材料粘合在含銅之金屬表 538080 六、申請專利範圍面前，用於處理金屬表面之組成物，該組成物包含 a. 2至60克/升過氧化氫； b . 5至360克/升硫酸； c .銹蝕抑制劑’其選自***，苯並***，咪唑，苯並咪唑，四唑及其任何之混合物； d .接著增強種類之來源，該加強種類選自鉬酸鹽、鎢酸鹽、鈮酸鹽、釩酸鹽及其任何之混合物。 29. 如申請專利範圍第 28項之組成物，其中銹鈾抑制劑包含在1-位置具吸電子能力強過氫基之吸電子基的苯並***。 30. 如申請專利範圍第 29項之組成物，其中銹蝕抑制劑爲1 -羥基苯並***。 31. —種提升聚合材料黏附含銅金屬表面之方法，該方法包含： a)使金屬表面與接著促進組成物接觸，其包含： 1. 2至60克/升過氧化氫； 2. 5至3 60克/升硫酸； 3. 銹蝕抑制劑，其選自***、苯並***、咪唑、苯並咪唑、四唑及其任意之混合物。； 4. 接著加強種類之來源，該加強種類選自鉬酸鹽、鎢酸鹽、鈮酸鹽、鉅酸鹽、釩酸鹽、I目、鎢、鉅、鈮、釩之異多酸或雜多酸，以及其任何 538080 t、申請專利範圍之混合物，及 b )使聚合物材料粘合在金屬表面。 32如申請專利範圍第3 1項之方法，其#中銹蝕抑制劑乃在1-位置具吸電子能力大於氫基之吸電子基的苯並三口坐 0 33.如申請專利範圍第3 2項之方法，其中銹蝕抑制劑乃 1 -羥基苯並***。538080 VI. Scope of Patent Application 〇 16. The composition of the scope of patent application No. 11 includes the source of halogen ions. 17. A composition for treating a metal surface before the polymer material is adhered to the metal surface, the composition comprising: a. 2 to 60 g / L hydrogen peroxide; b. 5 to 360 g / Liter of sulfuric acid; c. 1-hydroxybenzotriazole; d. A source of any subsequent reinforcing species selected from molybdate, tungstate, molybdate, niobate, vanadate, molybdenum , Tungsten, Giant, Niobium, Vanadium, Heteropoly or Heteropoly Acids, and Mixtures thereof. 18. The composition of item 17 in the scope of the patent application, wherein rhenium contains a rust inhibitor other than hydroxybenzotriazole. 19. The composition as claimed in claim 18, wherein the corrosion inhibitor is selected from the group consisting of triazole, benzotriazole, imidazole, benzimidazole, tetrazolium, and mixtures thereof. 20. The composition according to item 17 of the patent application scope, wherein the composition has an enhanced type and contains molybdate ions. 21. The composition according to item 17 of the scope of patent application, wherein the concentration of chlorine peroxide is 3 to 30 g / l. 22. A composition for treating a metal surface before the polymer material adheres to the metal surface, the composition comprising: 538080 VI. Patent application range a. 2 to 60 g / L of hydrogen peroxide; b · 5 to 3 60 g / l of sulfuric acid; c. Benzotriazole having an electron withdrawing group at the 1-position, the electron withdrawing ability of the electron withdrawing group is stronger than that of the hydrogen group. 23. The composition of claim 22, wherein the electron withdrawing group is selected from the group consisting of a hydroxyl group, an amine group, a nitro group, a sulfonic group, a carboxyl group, a halo group, a fluorenyl group and an unsaturated hydrocarbon group. 24. The composition of claim 22, wherein the benzotriazole is 1-hydroxybenzotriazole. 25. A method for improving the adhesion of a polymeric material to a copper-containing metal surface, including a) bringing the metal surface into contact with a composition, which comprises: 1.2 to 60 g / L of hydrogen peroxide; 2.5 to 360 g / Liters of sulfuric acid; 3. benzotriazole with an electron-withdrawing group at the 1-position, the electron-withdrawing ability of the electron-withdrawing group is greater than that of the hydrogen group; b) the polymer material is adhered to the metal surface. 26. The method of claim 25, wherein the electron withdrawing group is selected from the group consisting of a hydroxyl group, an amine group, a nitro group, a sulfonic group, a carboxyl group, a halo group, a fluorenyl group, and an unsaturated hydrocarbon group. 27. The method as claimed in claim 25, wherein the benzotriazole is 1-triphenylbenzotriD. 28 · —A composition comprising a polymer material bonded to a copper-containing metal table 538080 VI. A composition for treating a metal surface in the presence of a patent application, the composition comprising a. 2 to 60 g / liter Hydrogen oxide; b. 5 to 360 g / l sulfuric acid; c. Rust inhibitor 'selected from triazole, benzotriazole, imidazole, benzimidazole, tetrazole and any mixture thereof; d. Then enhancing the species Source, the reinforcing species is selected from molybdate, tungstate, niobate, vanadate, and any mixtures thereof. 29. The composition of claim 28, wherein the rust uranium inhibitor comprises a benzotriazole having an electron-withdrawing group having a strong hydrogen-absorbing group at the 1-position. 30. The composition of claim 29, wherein the rust inhibitor is 1-hydroxybenzotriazole. 31. A method for improving the adhesion of a polymeric material to a copper-containing metal surface, the method comprising: a) bringing the metal surface into contact with an advancing composition, comprising: 1.2 to 60 g / liter of hydrogen peroxide; 2.5 to 3 60 g / L sulfuric acid; 3. Rust inhibitor, selected from triazole, benzotriazole, imidazole, benzimidazole, tetrazole and any mixture thereof. ; 4. Then strengthen the source of the species selected from the group consisting of molybdate, tungstate, niobate, giant salt, vanadate, I, tungsten, giant, niobium, vanadium heteropoly acid or heteropoly Polyacid, and any of its 5,380,80 t, patent-pending mixtures, and b) bonding polymer materials to the metal surface. 32. The method according to item 31 of the scope of patent application, wherein the rust inhibitor in # is a benzotriazole with an electron withdrawing ability greater than the hydrogen group at the 1-position. 33. As the item 32 in the scope of patent application The method wherein the rust inhibitor is 1-hydroxybenzotriazole.